CN105646865B - A kind of carbon dioxide preserves the fast synthesis method of material - Google Patents

A kind of carbon dioxide preserves the fast synthesis method of material Download PDF

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Publication number
CN105646865B
CN105646865B CN201410578343.6A CN201410578343A CN105646865B CN 105646865 B CN105646865 B CN 105646865B CN 201410578343 A CN201410578343 A CN 201410578343A CN 105646865 B CN105646865 B CN 105646865B
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carbon dioxide
preserves
polyalcohol
ethylenediamine
gas
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CN105646865A (en
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张建斌
郭波
赵天翔
李强
李立华
沙峰
张飞
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Inner Mongolia University of Technology
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Inner Mongolia University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention is to be based on greenhouse gases CO2Trapping and Fast back-projection algorithm carbon dioxide preserve material (CO2SM method).The method adds a small amount of water, the CO towards in various types of desulfurization flue gas, industrial waste gas and raw material of industry gas using cheap ethylenediamine and glycols polyalcohol as main system2, fast and efficiently composite solid state CO2SM, after being handled through organic solvents such as ethanol, dichloromethane, chloroforms, CO is obtained through filtering, vacuum drying2SM powders.Test result indicates that, the material can be with CO3 ‑Form store a large amount of CO2, it is relatively stable at room temperature, it can serve as chemical fertilizer and ultra-fine CaCO3Synthesis material, can also heat the high-purity CO of acquisition2And regenerating system.Because it is to CO2With trapping is quick, storage capacity is big, regenerability is good and synthesizes the advantage such as with low cost, can be greatly promoted CO2Trap, preserve and using the development of technology, while can be with large-scale industrial production, and then the new material that preserves is promoted in CO2Trapping is with utilizing the research and application in terms of technology, chemical fertilizer.

Description

A kind of carbon dioxide preserves the fast synthesis method of material
Technical field
The present invention is to be based on greenhouse gases CO2Trapping and Fast back-projection algorithm carbon dioxide preserve material (CO2SM method). Belong to environmental protection and new preserve field of material technology.
Background technology
Global warming turns into international hot spots, CO2Cause the whole world because having greenhouse effects to be generally considered One of major reason of climate warming.How CO is reduced2CO in discharge, reduction air2Concentration is the common difficulty of facing mankind. Combustion process is CO2The largest source of discharge, wherein only coal fired generation process discharge capacity accounts for whole world burning same fuel discharge capacity 30%~40%, therefore control and slow down CO in combustion process2Discharge is asked for solving global warming and greenhouse effects Topic is significant.
In recent years, the researcher of various countries is in CO2The input for trapping and sealing up for safekeeping (CCS) technical elements is very big, and the technology is more It is related to absorption and sorption and membrane separation technique.However, CO2Trapping and utilization (CCU) technology but slower development, CCU technologies are maximum Development obstacles be mainly CO2Molecule has high thermodynamic stability, it is necessary to which the compound of more upper state deactivates CO2Come real Existing CO2Fixation.Due to CO2Wide material sources, if process economy and can obtain high value added product, CCU technologies will be obtained quickly Development.Therefore, researcher has been developed passes through chemokinesis CO with one-level, secondary amine2Produce carbaminate and its spread out Biology, next to that preparing the products such as carbamate or polyurethane by the method for HTHP, but exists as molten more process The shortcomings of degradable degeneration of agent high volatile, amine, high energy consumption of process.Therefore, we select glycols polyalcohol as amine Fixative, effective fixation of amine is realized with the interaction of alcoholic extract hydroxyl group and amido, while strengthening system trapping CO2Property Can, regeneration energy consumption is reduced, corrosivity of the system to equipment is reduced, and then development is based on this fast and efficiently CO2Technique for fixing, The CO of high storage capacity is prepared simultaneously2SM powders, this is for China CO2Emission reduction and its using technology development have it is very important Practical significance.
The content of the invention
Carbon component is caught using ethylenediamine and glycols polyalcohol to be main it is an object of the invention to provide one kind, addition is a small amount of CO in water, rapid acquiring industrial gasses (predominantly various types of desulfurization flue gas, industrial waste gas and raw material of industry gas)2Come Prepare CO2SM method.
Present invention trapping CO2And Fast back-projection algorithm CO2SM method, to total CO in carbonaceous gas2Content does not have special want Ask, still, in order to reach more preferable decarburization effect, preferably various types of desulfurization flue gas, industrial waste gas and the raw material of industry CO in gas2Content should be greater than 8% (vol.).
In ethylenediamine of the present invention and glycols polyalcohol trapping CO2In method, process conditions are not limited strictly, but Preferential to use ordinary-pressure absorption, it is preferably room temperature~80 DEG C to absorb temperature.
Described glycols polyalcohol mainly includes ethylene glycol, propane diols, glycerine, butanediol, diethylene glycol, three second The different polymerization degrees such as glycol, polyethylene glycol 100, polyethylene glycol 200, Liquid Macrogol, polyethylene glycol 400, Macrogol 600 Polyethylene glycol.
The general principle of the present invention can be illustrated with following several ways：
After ethylenediamine-glycols polyol systems are prepared, water of the addition less than 10% (wt), it traps CO2Base Present principles are as follows：
Containing CO2Various types of desulfurization flue gas, industrial waste gas and raw material of industry gas and ethylenediamine-glycols it is many During first mixed alkoxide solution contact, occurs following effect：
(1) solid amine effect：
R-NH2+ HO-R '=R-N (H2)…HO-R’ (1)
And/or R-NH2+ HO-R '=R-NH2…(H)O-R’ (2)
And/or R-NH2+ HO-R '=R-NH3 +-O-- R ' (fixation of amine) (3)
(2) CO is trapped2, synthesis CO2SM：
[R-N(H2)…HO-R’]+CO2=RNH3CO3R’ (4)
And/or R-NH2…(H)O-R’+CO2=RNH3CO3R’ (5)
And/or R-NH3 +-O--R’+CO2=RNH3CO3R’ (6)
By above-mentioned mechanism, CO is realized2SM's is effectively synthesized.
Embodiment
The polynary alcohol-water system trapping of ethylenediamine-glycols of the present invention is described with reference to specific embodiment CO2And prepare CO2SM methods.
Embodiment 1：
At 35 DEG C, 20g ethylenediamines are dissolved in 80g polyethylene glycol, and add 3g water to eliminate the foaming phenomena of process.With 400ml/min gas flow rate is passed through into solution containing 12% (vol.) CO2Gas, is continuously passed through 3h, is entered with absolute ethyl alcohol Row washing, filtering, 2h is dried in vacuo at 60 DEG C, obtains CO2SM powders.
The main physico-chemical property of product：
Particle diameter is (20~30) μm, and 100d is placed in air and is never degenerated, 90 DEG C of fusing point, 100 DEG C of decomposition point.FTIR light Modal data：2183cm-1；R-NH3 +Characteristic peak, 1570cm-1And 1483cm-1；-CO2 -。13C NMR spectra data：164.45ppm；- CO3 -.XRD：-NH-COO-；17.58°、21.54°、22.46°、22.58°、29.30°、35.35°.
Embodiment 2：
At 25 DEG C, 20g ethylenediamines are dissolved in into 40g ethylene glycol and 5g water is added to eliminate the foaming phenomena of process.With 300ml/min gas flow rate is passed through pure CO into solution2Gas, is continuously passed through 1.5h, is washed with dichloromethane, mistake Filter, 2h is dried in vacuo at 40 DEG C, obtains CO2SM powders.
The main physico-chemical property of product：
Particle diameter is (20~30) μm, and 100d is placed in air and is never degenerated, 94 DEG C of fusing point, 106 DEG C of decomposition point.FTIR light Modal data：2175cm-1；R-NH3 +Characteristic peak, 1576cm-1And 1489cm-1；-CO2 -。13C NMR spectra data：164.26ppm；- CO3 -.XRD：-NH-COO-；17.54°、21.44°、22.49°、22.60°、29.32°、35.33°.
Embodiment 3：
At 30 DEG C, 20g ethylenediamines are dissolved in into 30g butanediols and 5g water is added to eliminate the foaming phenomena of process.With 400ml/min gas flow rate is passed through pure CO into solution2Gas, is continuously passed through 1h, washed, filtered with chloroform, 2h is dried in vacuo at 60 DEG C, CO is obtained2SM powders.
The main physico-chemical property of product：
Particle diameter is (20~30) μm, and 100d is placed in air and is never degenerated, 91 DEG C of fusing point, 102 DEG C of decomposition point.FTIR light Modal data：2188cm-1；R-NH3 +Characteristic peak, 1572cm-1And 1488cm-1；-CO2 -。13C NMR spectra data：164.37ppm；- CO3 -.XRD：-NH-COO-；17.54°、21.49°、22.55°、22.63°、29.32°、35.33°.

Claims (4)

1. a kind of carbon dioxide preserves the synthetic method of material, it is characterised in that using ethylenediamine and polyalcohol as main system, simultaneously A small amount of water is added, the CO in industrial waste gas and raw material of industry gas is trapped with this2, simultaneously synthesizing solid carbon dioxide preserves material Feed powder body, is comprised the following steps that：
(1) it by ethylenediamine and polyalcohol is (30-70) in molar ratio to be first: (25-75) is mixed, and addition is less than 10wt% Water, stirs at room temperature~80 DEG C；
(2) it is passed through containing CO2More than 8 volume % mixed gas, material is preserved through 60~360min formation carbon dioxide；
(3) material is preserved with ethanol, dichloromethane or chloroform processing carbon dioxide, then through vacuum at filtering, 40~75 DEG C It is dried to obtain carbon dioxide and preserves material powder；
The polyalcohol include ethylene glycol, propane diols, glycerine, butanediol, diethylene glycol, triethylene glycol, polyethylene glycol 100, At least one of polyethylene glycol 200, Liquid Macrogol, polyethylene glycol 400 and Macrogol 600.
2. a kind of carbon dioxide according to claim 1 preserves the synthetic method of material, it is characterised in that the main body system For ethylenediamine and the mixed solution of polyalcohol.
3. a kind of carbon dioxide according to claim 1 preserves the synthetic method of material, it is characterised in that inhaled using normal pressure Receive, absorption temperature is room temperature~80 DEG C, product carbon dioxide preserves material for ethylenediamine-polyalcohol-CO2Copolymer, trapping CO2With-CO3 -Form be stored in material.
4. a kind of carbon dioxide according to claim 1 preserves the synthetic method of material, it is characterised in that the Industry Waste Gas is desulfurization flue gas.
CN201410578343.6A 2014-10-24 2014-10-24 A kind of carbon dioxide preserves the fast synthesis method of material Active CN105646865B (en)

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CN108409960B (en) * 2017-11-01 2020-10-09 内蒙古工业大学 Method for synthesizing polyurethane by utilizing carbon dioxide reservoir material
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Citations (3)

* Cited by examiner, † Cited by third party
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CN1780677A (en) * 2003-04-04 2006-05-31 得克萨斯大学体系董事会 Polyamine/alkali salt blends for carbon dioxide removal from gas streams
CN101130151A (en) * 2006-08-23 2008-02-27 辽宁省燃烧工程技术中心 Method for reducing emission of flue gas carbonic anhydride of fire coal electric power plant and recycle, and special system thereof
CN103007687A (en) * 2012-12-07 2013-04-03 中国科学院过程工程研究所 Method for inhibiting degradation of decarburization amine absorbent

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US9440182B2 (en) * 2008-12-24 2016-09-13 General Electric Company Liquid carbon dioxide absorbents, methods of using the same, and related systems
JP5901296B2 (en) * 2012-01-06 2016-04-06 三菱日立パワーシステムズ株式会社 CO2 chemical absorption system

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1780677A (en) * 2003-04-04 2006-05-31 得克萨斯大学体系董事会 Polyamine/alkali salt blends for carbon dioxide removal from gas streams
CN101130151A (en) * 2006-08-23 2008-02-27 辽宁省燃烧工程技术中心 Method for reducing emission of flue gas carbonic anhydride of fire coal electric power plant and recycle, and special system thereof
CN103007687A (en) * 2012-12-07 2013-04-03 中国科学院过程工程研究所 Method for inhibiting degradation of decarburization amine absorbent

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